Electrochemically generated tungsten‐based active species as catalysts for metathesis‐related reactions: 1. Acyclic diene metathesis polymerization of 1,9‐decadiene

Abstract

Electrochemically generated tungsten-based active Electrochemically generated tungsten-based active species as catalysts for metathesis-related reactions: 1. species as catalysts for metathesis-related reactions: 1. Acyclic diene metathesis polymerization of 1,9-decadiene Acyclic diene metathesis polymerization of 1,9-decadiene Okan Dereli, Bu È lent Du È z, Birgu È l Zu È mreog AE lu-Karan* and Yavuz I Ç mamog AE lu* Hacettepe University, Chemistry Department, 06532 Ankara, Turkey The application of the WCl 6 ±e À ±Al±CH 2 Cl 2 system to acyclic diene metathesis polymerization of 1,9-decadiene is reported. The polyoctenamer formed is of a weight-average molecular weight of 9000 with a polydispersity of 1.92. IR and NMR spectral analyses indicate the retention of the double bonds in the polymer structure with high trans content as expected from a step condensation reaction. This relatively stable catalytic system, however, also activates the competing vinyl addition reactions while being inactive in ring-closure metathesis reactions.

Application of electrochemically generated molybdenum-based catalyst system to the ring-opening metathesis polymerization of norbornene and a comparison with the tungsten analogue

“…This ratio has been previously found as 125 for the tungsten-based catalyst system. 29 Figures 1 and 2 show the influences of different reaction times and electrolysis times on the amount of polynorbornene for electrochemical molybdenum-and tungsten-based systems. Polymerization conversion first increased with reaction time and reached a plateau value at around 4 min.…”

“…29 This electrochemical tungsten-based catalyst produced a mainly cis-polynorbornene (σ c = 0.61) with high conversions and at short periods. In this study we describe the application of the MoCl 5 -e − -Al-CH 2 Cl 2 system to the ROMP of norbornene and compare the results, in terms of the reaction conditions and polymer microstructure with those previously observed with the tungsten analogue.…”

Ring‐opening metathesis polymerization of cyclododecene using an electrochemically reduced tungsten‐based catalyst

“…In the 13 C NMR Materials, Nanoscience and Catalysis spectrum, all peaks of the polymer are in the same position as those observed previously. 14 The peak positions for the 13 C NMR spectrum of polydodecenamer are given in Table 2. The olefinic region (129-131 ppm) clearly confirms the formation of polymers by metathesis (Fig.…”

Electro-Induced Early Transition Metal Metathesis Catalyst Systems for the Production of Polyacetylene

“…21,22 We previously reported many scientific studies on the application of WCl 6 -e À -Al-CH 2 Cl 2 catalyst system to olefin metathesis reactions [23][24][25][26][27][28][29] but only one study on MoCl 5 -e À -Al-CH 2 Cl 2 catalyst system to ROMP of norbornene. 30 In this paper we described the synthesis of ROMP of COT with the electrochemically generated W and Mo-based catalyst.…”

“…The major advantages of these catalyst systems (WCl 6 -e À -Al-CH 2 Cl 2 and MoCl 5 -e À -Al-CH 2 Cl 2 ) electrochemically generated are easily preparation and higher selectivity. These systems are easily obtained and distinguished from the wellknown molybdenum and tungsten alkylidenes by being less sensitive to atmospheric oxygen and retaining its activity for about 10 h. 24 …”